The permeability and stability of Sm0.7Sr0.3CoO3−δ (SSCO) regarding the special requirements for carbon capture and storage (CCS) application were investigated. Pure CO2 was used as the sweep gas at 900 °C, leading to that the oxygen permeation flux decreases by about 34 %. Several cycles of changing the sweep gas between helium and CO2 indicate the good reversibility of this degradation. Both carbonate formation and adsorption of CO2 on the membrane surface are responsible for the degradation of the membrane performance. The better CO2 resistance results from the substitution of Sm for Sr due to the higher acidity of Sm2O3 (1.278) than that of SrO (0.978) and a discontinuous layer of carbonate.